CN108604663A - The method for producing lithium film - Google Patents

The method for producing lithium film Download PDF

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Publication number
CN108604663A
CN108604663A CN201680070010.XA CN201680070010A CN108604663A CN 108604663 A CN108604663 A CN 108604663A CN 201680070010 A CN201680070010 A CN 201680070010A CN 108604663 A CN108604663 A CN 108604663A
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Prior art keywords
lithium
lithium metal
metal film
substrate
cathode
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Inventor
埃米莉·博杜因
拉里·斯旺格
奥尔哈·马什塔利日
米尼·恩古延
斯蒂芬·奥布赖恩
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Research Foundation of City University of New York
Clean Lithium Corp
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Research Foundation of City University of New York
Clean Lithium Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
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    • H01M4/06—Electrodes for primary cells
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

Present disclose provides a kind of high-purity lithium metal film and a kind of methods for controlling high-purity lithium metal film morphology.In general embodiments, present disclose provides the high-purity lithium metal films with controlled thickness and form.High-purity lithium metal film is produced by using selective lithium ion conduction layer electrolytic deposition lithium.The form of lithium metal film can be controlled by changing the current rate for deposition.The lithium metal film of the present invention advantageously provides high-purity lithium metal film, as expected the wherein thickness of film and/or form can be applied and change.

Description

The method for producing lithium film
Technical field
The disclosure relates generally to a kind of high-purity lithium metal film with special properties.More specifically, the disclosure relates to And the high-purity lithium metal film with controlled thickness and form.High-purity lithium metal film has 10nm to the thickness of hundreds of microns And the form selected from smooth film, nanoparticle and nanometer rods.
Background technology
Lithium metal is due to its high theoretical specific capacity (3860mAh/g), low-density (0.59g/cm3) and low negative reduction potential (- 3.040 comparison SHE) but a kind of promising high energy density cells anode material.Lithium metal has been routinely used for once In battery, and secondary cell then typically uses lithium intercalated graphite anode.This graphite anode is replaced to can be provided in lithium metal Greatly improving in terms of the energy density of battery, this is because the theoretical capacity of lithium metal is ten times of height of graphite.
However, safety problem, recyclability difference and short life limited lithium metal its current Anodic cycle The use being necessary in secondary cell application.These problems are mainly that (underlying metal contains since the purity of lithium metal is insufficient In terms of amount, form nitride and oxide with lithium in air reacts aspect, and other problems related with impurity) and The formation of dendrite on lithium metal surface.These problems can by using with it is smooth, uniform, without dendrite and without lithium field trash High-purity lithium metal solve.
For battery applications, lithium metal is used in the form of foil mostly.Lithium foil is traditionally using electrolysis process with lithium chloride It is manufactured by lithium carbonate as precursor.For example, describe the United States Patent (USP) 4,274,834 of electrolysis process in Brown et al., Lithium carbonate is converted into lithium chloride by being reacted with hydrochloric acid, then passes through (380 DEG C to 400 DEG C) reduction lithium chlorides of high temperature and potassium chloride Eutectic compound forms the blocky lithium metal recycled usually as ingot.
Another electrolysis process for producing lithium foil is described in the United States Patent (USP) 4,724,055 of Le Roux et al..It is beautiful State's patent 4,724,055 is related to preparing the continuous processing of lithium by lithium chloride contained in electrolyzing fused salt mixture.The technique A large amount of energy is undesirably consumed, and generates extremely corrosive and toxic air pollutants chlorine as by-product, this is needed Want additional purifying/security step.
In order to form the lithium foil with the thickness between 50 μm and 200 μm, lithium metal ingot is by squeezing out or in air Rolling is machined (usually in low wet gas environments in the nitrogen/oxygen reacted with lithium metal).However, this is undesirable More pollutants are introduced to final product by ground.Made foil is cut into desired size and shape, and is attached to collection Electric body (typically copper foil), with the anode being further used as in a lithium metal battery.
The conventional method for forming lithium foil or film uses high-purity lithium metal as precursor and carries out or need under reduced pressure The additive of limitation lithium deposition that will be additional.For example, (also referred to as being sputtered) by physical vapour deposition (PVD) (PVD), vacuum Evaporation, laser ablation and ion plating prepare the smooth lithium film of high metal purity, such as the European patent 1,174 of Kugai et al., The United States Patent (USP) 7,629,083B2 of 936 and Cho et al..PVD technique can produce the high-purity lithium gold in 1-200 micron ranges Belong to film, but this method needs 1.33 × 10-4Pa(1×10-6Support) or lower pressure, this is because under partial vacuum The oxidation or degradation of alkali metal film may occur due to moisture.
Present disclose provides a kind of methods that can generate the lithium metal film without dendrite with controlled thickness and form. The lithium metal film of no dendrite is smooth and can directly be produced from carbonic acid lithium source.
Invention content
It is deposited in conductive substrate for manufacture present disclose provides a kind of and there is controlled thickness and form High-purity lithium metal film process.The disclosure additionally provides a kind of for manufacturing the lithium metal film based on high-purity, without dendrite The method of electrode, the electrode can be without any additional process for primary and two level lithium metal battery, to simplify battery Manufacturing process.
In general embodiment, present disclose provides a kind of no dendrite and optically smooth lithium metal films.Lithium gold Belong to film to be electrolysed lithium deposition on cathode by using selective lithium ion conduction layer and obtain.The form of lithium metal film can lead to It crosses and changes the current rate for deposition to control.
In one embodiment, lithium metal film has about 1nm to about 1000 μm of thickness.Lithium metal film can have about 1nm or higher and less than about 40 μm of thickness.Specifically, lithium metal film can be with about 25 μm of thickness.
In one embodiment, lithium metal film has smooth configuration of surface.
In another embodiment, lithium metal film includes spherical structure.
In one embodiment, lithium metal film includes compact autoregistration nanorod structure.The advantages of nanometer rods form, exists In relative to the current supply of lithium, compact uniform nanometer rods can significantly reduce the real table area of lithium anode.This is beneficial , it is made because the reduction of the surface area of anode reduces due to chemistry and electrochemical reaction in battery between lithium and electrolyte At lithium loss.Compared with traditional electrode, this special form can improve capacity, recyclability and reduce impedance.
In one embodiment, the present invention provides a kind of lithium metal films, optically with regard to d<For λ/(8cos θ) It is smooth, wherein d is surface roughness (such as the r.m.s. roughness height measured from reference planes), and λ is incident light Wavelength (200-1000nm), and θ is the incidence angle of incident light.
In one embodiment, present disclose provides a kind of electrodes comprising：Substrate and the lithium metal provided on substrate Film.Lithium metal film does not have dendrite and is optically smooth.
In one embodiment, substrate includes the material at alloy not with lithium.Substrate may include being selected from copper and stainless steel Material.
In one embodiment, before providing lithium metal film on substrate, by the concentrated sulfuric acid (98 weight %) It etches substrate two seconds, substrate is rinsed with deionized water and is air-dried substrate to be pre-processed to the substrate.
In one embodiment, a kind of lithium alloy is provided.The lithium alloy includes substrate and the lithium provided on substrate gold Belong to film.The lithium metal film does not have dendrite and is optically smooth, and substrate includes the material with lithium at alloy.
In one embodiment, substrate includes the material at alloy with lithium.Substrate may include aluminium, tin, silicon or it is any its It is with lithium at the metal of alloy.
In one embodiment, battery is provided, and the battery includes cathode, anode and electrolyte.In cathode and sun At least one upper offer lithium metal film of pole.Lithium metal film does not have dendrite and is optically smooth.
In one embodiment, battery is lithium primary battery, chargeable lithium metal battery or minicell.
In one embodiment, present disclose provides a kind of methods for the desired form obtaining lithium metal film.The party Method includes it is expected using selective lithium ion conduction layer electrolytic deposition lithium metal, and the current rate of control electrolytic deposition Form.
In one embodiment, current rate is controlled in 1mA/cm2To 10mA/cm2In the range of.
One advantage of the present disclosure is to provide the high-purity lithium metal film with controlled thickness and form.Lithium metal film makes It is obtained with selective lithium ion conduction layer.By by thickness and form control in the desired range in, lithium film can easily by Designed for specific application.
Another advantage of the disclosure is to provide a kind of for controlling the form of the high-purity lithium metal film of electrolytic deposition Method.High-purity lithium metal film is optically smooth and without dendrite, and therefore can be used for needing the smooth lithium metal film of high-purity Battery and other application.
Additional feature and advantage are illustrated herein, and will be bright from specific implementation mode below and attached drawing Show.
Description of the drawings
Fig. 1 shows the schematic front of lithium production unit structure disclosed in U.S. Patent Publication 2015/0014184A1 Figure；
Fig. 2 shows the exemplary details figures of the lithium production unit structure of Fig. 1；
Fig. 3 shows the schematic exploded detail view of the lithium production unit of U.S. Patent Publication 2015/0014184A1；
Fig. 4 shows the SEM image of the lithium film of electrolytic deposition；
Fig. 5 is shown with different -1, -3, -5, -10 and -15mA/cm of current rate2Lithium film of the electrolytic deposition in copper substrate Photo；
Fig. 6 shows the lithium deposition on the copper dish electrode (1 3/8 " diameter) during 45 minutes 4 hours in polishing.
Specific implementation mode
The U.S. Patent Publication 2015/0014184A1 of Swonger describes a kind of for connecting from lithium carbonate or other lithium salts The electrolysis process of continuous production lithium metal, these lithium carbonates or other lithium salts dissociate in acidic electrolyte bath and by the non-lithium portions of raw material It is allocated as discharging for gas.Swonger electrolysis process is using aqueous acidic electrolyte and lithium production unit structure with continuous from lithium salts Produce lithium metal.Lithium production unit structure include cell cube, cathode, the electrolyte aqueous solution containing lithium ion and anion and Composite layer between embedded cathode and electrolyte aqueous solution.The composite layer includes li-ion conductive glass ceramics (LIC- GC the lithium-ion-conducting barrier film (LI-BF)) and by the lithium for forming cathode being isolated with electrolyte aqueous solution.LIC-GC-BF is multiple Closing object allows directly to produce lithium metal from solution, and lithium metal is deposited directly on clean cathode, is carried without additional Taking technique.
Figures 1 and 2 show that the lithium production technology of 2015/0014184 A1 of U.S. Patent Publication, wherein the electrolysis of rich lithium Mass flow crosses extraction unit.When applying potential to system, lithium metal is gathered on the swap cathode below embedded composite layer. Fig. 1 shows the schematic elevational view of lithium production unit structure, and Fig. 2 is the exemplary details figure of the cellular construction of Fig. 1.
In fig. 1 and 2, electrolysis cells 10 include upper curtate 12 and lower curtate 14.Unit 10 is characterized in that removable 16 crosscutting tool of cathode cross section.The Axis Cross of cathode 16 and unit 10, when cell reaction is happened at 16 top of cathode Electrolyte 18 in when advance, pass through LIC-GC-BF composite layers.Anode 20 is provided to unit upper curtate 12.On cathode 16 The unit section 12 of side loads electrolyte 18 via entrance 22, carries out electrolysis and via 24 discharge waste cell melt of outlet.Cathode 16 composite layer 28 by being embedded between cathode 16 and electrolyte 18 is contacted with electrolyte 18.Composite layer 28 includes and electricity The adjacent li-ion conductive glass ceramics layer of solution matter 18 (LI-GC) 30 and the lithium ion that is placed between ceramic layer 30 and cathode 16 Conductibility barrier film (LI-BF) 32.Compound 28 including barrier layer 32 and glass-ceramic layer 30 by cathode 16 formed Lithium is isolated with electrolyte 18.It is formed with lithium metal and is deposited on advance cathode 16 across composite layer 28, axis 26 promotes the moon Pole 16 and compound 28.The lithium metal generated at solid state cathode 16 can be used as proof gold symbolic animal of the birth year to extract out.
Suitable 18 ingredient of electrolyte includes water-soluble lithium salts, including but not limited to Li2CO3And LiCl.In order to improve dissolving Lithium salts is dissolved in hydration acid such as sulfuric acid by degree, and as electrolyte 18 in electrolysis cells 10.Lithium carbonate (Li2CO3) it is most The raw material of the lithium salts that is easy to get and the initial trial that is used as unit 10.
2015/0014184 A1 of U.S. Patent Publication teaches the use of sulfuric acid for efficiently producing lithium metal from lithium carbonate Be important, this is because lithium carbonate is substantially insoluble in water and organic solvent, and lithium carbonate have in sulfuric acid solution it is much higher Solubility.By dissociating lithium carbonate and only lithium ion being placed in solution, electrolyte solution keeps stablizing and will not cause The accumulation of the concentration of the non-lithium ion part of raw material.Lithium carbonate can be continuously fed into the tank outside electrolysis cells, is discharged The CO discharged by electrolyte sulfuric acid2Gas and from cathode collector lithium metal.This can operate continuously or be carried out as batch process.
U.S. Patent Publication 2015/0014184A1 is disclosed：Some suitable components suitable for its electrolysis cells 10 are Illustrated in 2013/0004852 A1 of U.S. Patent Publication.
Cathode 16 is characterized in that embedded compound (Li-GC/Li-BF) 28, it means that compound 28 be inserted into or It is placed between cathode 16 and electrolyte 18.Cathode 16 advances along the axis of unit 10 so that the lithium generated leaks through compound 28 and make cathode deposition lithium be isolated.Cathode 16 includes and the nonreactive suitable material of lithium metal and composite layer.Li- GC/Li-BF composite layers 28 are the constant resistance portions between anode chamber and the lithium metal formed on cathode.Movable cathode is with suitable Answer the lithium metal layer continuously thickened on cathode.
As disclosed in U.S. Patent Publication 2015/0014184A1, composite layer (Li-GC/Li-BF) 28 wraps Include li-ion conductive glass ceramics layer (LI-GC) 30 and lithium-ion-conducting barrier film (LI-BF) 32.It is substantially impermeable Layer (LI-GC) 30 can be active metallic ion conductibility glass or glass ceramics (for example, lithium-ion-conducting glass-pottery Porcelain, the stability with high active metallic ion conductibility and pair with the aggressive electrolyte of lithium metal vigorous reaction.It closes Suitable material is substantially impermeable, ionic conductivity, and with aqueous electrolyte or other electrolyte (catholytes Matter) and/or cathode material be chemical compatibility (otherwise its can adversely be reacted with lithium metal).These glass or glass ceramic material It there is no gap, not swellable and its presence of ionic conduction property independent of liquid electrolyte or other reagents. They also have high ion conductivity, at least 10-7S/cm, generally at least 10-6S/cm, for example, at least 10-6S/cm to 10-4S/ Cm, and up to 10-3S/cm or higher are at least 10 to the overall ionic conductivity of protection multilayer structure-7S/cm and height Up to 10-3S/cm or higher.The thickness of layer is preferably from about 0.1 to 1000 micron, or in the ionic conductivity of layer is about 10-7S/ Be about 0.25 to 1 micron in the case of cm, or layer ionic conductivity about 10-4To about 10-3In the case of between S/cm It is about 10 to 1000 microns, preferably 1 to 500 micron, more preferable 50 to 250 microns, for example, about 150 microns.
The example of glass-ceramic layer (LiC-GC) 30 includes glassy state or amorphous metal ion conductors, such as phosphorus base glass Glass, oxide-based glasses, phosphorus-nitrogen oxides base glass, sulfenyl glass, oxide/sulfide based glass, selenium base glass, gallium base Glass, germanium base glass or Pyrex (for example, see DP Button et al., Solid State Ionics, Vols.9-10, Part 1,585-592, December nineteen eighty-three), ceramic active metal ion conductors, such as beta-alumina lithium, beta-alumina sodium, Li superionic conductors (LISICON), Na superionic conductors (NASICON) etc.；Or the active metal ion conductors of glass ceramics.Tool Body example includes LiPON, Li3PO4、Li2S、SiS2、Li2S、GeS2、Ga2S3And Li2O。
Suitable LiC-GC materials include the lithium-ion-conducting glass for having following composition in mole percent Ceramics：P2O526-55%；SiO20-15%；GeO2+TiO225-50%；Wherein GeO20-50%；TiO20-50%；ZrO2 0-10%；M2O30-10%；Al2O30-15%；Ga2O30-15%；Li2O3- 25%, and contain following principal crystalline phase： Li1+x(M,Al,Ga)x(Ge1-yTiy)2-x(PO4)3, wherein X≤0.8 and 0≤Y≤1.0, and wherein M be selected from Nd, Sm, Eu, The element of Gd, Tb, Dy, Ho, Er, Tm and Yb；And/or Li1+x+yQxTi2-xSi3P3-yO12, wherein 0<X≤0.4 and 0<Y≤0.6, And wherein Q is Al or Ga.Other examples include 11Al2O3、Na2O11Al2O3、(Na,Li)i+xTi2-xAlx(PO4)3(0.6≤ X≤0.9) and the relevant structure of crystallography, Na3Zr2Si2PO12、Li3Zr2Si2PO4、Na5ZrP3O12、Na5TiP3O12、 Na3Fe2P3O12、Na4NbP3O12、Li5ZrP3O12、Li5TiP3O12、Li5Fe2P3O12And Li4NbP3O12And combination thereof, it can Selection of land is sintered or melting.Ceramic ion active metallic ion conductor appropriate is described in the United States Patent (USP) of such as Adachi et al. In 4,985,317.
2015/0014184 A1 of U.S. Patent Publication is disclosed：Suitable LiC-GC materials further include coming from Ohara companies The product of (Kanagawn, Japan), trade mark LIC-GCTM、LISICON、Li2O--Al2O3--SiO2--P2O5--TiO2(LATP) with And other have the material of similar high metal-lithium ion conductivity and environment/chemical resistance, the material manufactured such as Ohara et al. Material etc..For example, see United States Patent (USP) 8,476,174.United States Patent (USP) 8,476,174 is disclosed including at least with LiTi2P3O12 The glass ceramics of the crystal of structure, the crystal meet 1<IA113/IA104≤ 2, wherein IA104It is point by X-ray diffraction measure The peak strength of the dispensing indices of crystallographic plane 104 (2 θ=20 to 21 °), and IA113It is allocated to the indices of crystallographic plane 113 (2 θ=24 to 25 °) Peak strength.
The lithium-ion-conducting barrier film 32 (Li-BF) of 2015/0014184 A1 of U.S. Patent Publication is that have high lithium gold Belong to the lithium metal ionic conductivity film or coating of ionic conductivity (typically 1.0mS/cm to 100mS/cm).High-lithium ion moves Move number (t+) it is preferred.Low t+Li+Electrolyte then due to allow battery unit in ion concentration gradient and cause high internal resistance from And performance is hindered, this may limit battery unit service life and limitation reduction rate.In t+=0.70 and t+Migration between=1.0 Number is preferred.Lithium-ion-conducting barrier film is not reacted with lithium metal and LI-GC materials.
LI-BF films 32 include active metal compound, wherein " active metal " be used as the lithium of battery active material, sodium, Magnesium, calcium and aluminium.Suitable LI-BF materials include active metal and Cu3N, active metal nitrides, active metal phosphides, work Property metal halide, active metal phosphorus chalcogenide glass and active metal phosphorus nitrogen oxides glass (Cu3N、Li3N、Li3P、LiI、 LiF, LiBr, LiCl and LiPON) recombination reaction product.U.S. Patent Publication 2015/0014184A teaches LI-BF materials It must also prevent the dendrite due to being formed on cathode with LI-GC materials.This can be by between cathode and LI-GC It establishes physical distance and/or dendrite is provided and be not easy the physical barriers portion penetrated to realize.A kind of preferred LI-BF films are by Kim Et al. in scientific report (Scientific Reports) (article number：1917doi:10.1038/srep01917) description The conduction leading by the irreversible gelation of in-situ heat and single ion caused by physics organogel electrolyte.The electrolysis Matter has the conductivity and t of 8.63mS/cm at room temperature+=0.84.This organogel electrolyte can be arranged in perforated membrane To provide additional structure and dendrite penetration resistance in shape object.Typical porous membranoid substance thickness is 1 μm to 500 μm, such as 20 μ m.Acceptable porous membranoid substance includes the HIPORE polyolefin flat membrane-manufactured by Asahi Kasei E-materials companies Membranoid substance.
The continuous lithium metal production technology of 2015/0014184 A1 of U.S. Patent Publication can use not expensive carbonic acid Lithium, or lithium ion source of equal value is come directly from for the acid solution by drawing lithium metal in spodumene ore or other natural lithium sources In directly produce lithium metal.
The unit schematically shown in Fig. 3 is utilized in the illustrative processes of 2015/0014184 A1 of U.S. Patent Publication.It is single Member 110 includes unit cover 116, retainer 118, Pt anodes 112, cathode 124 and with to be incorporated into porous polyolefin flat membrane-membranaceous The LiC-GC conductibility glass 114 of lithium-ion-conducting barrier film 120 in object 122.LiC-GC-BF multilayers supported are embedding Enter between cathode 124 and the electrolyte 18 of rich lithium ion (as illustrated in fig. 1 and 2).Unit further includes the support for having washer 128 PropertyTube-in-tube structure 126.One washer is sealed between LiC-GC and shell, to prevent electrolyte from anode chamber It leaks into cathode chamber.Another washer makes it possible to carry out homogeneous compaction to LiC-GC to prevent LiC- by Teflon sleeves GC plates are damaged.
Unit 110 includes anode 112, is the Ni―Ti anode of platinum plating, 1 " × 4 " rhodium and the plating of palladium jewelry.Cathode is internal system The palladium cathode disc for 1.4 inch circulars made.114 materials of LiC-GC are 150 μ m-thicks, 2 inch circularsG71- 3N33：2IN × 150 μm DIA are cast body, come from Ohara companies, 23141 A Luoyue Vists, and Lan Qiaosheng Margaritas add Li Funiya 92688.
Lithium-ion-conducting gel electrolyte 120 is by following manufacture：Scientific and technical research is stood by the luxuriant mountain country of Ulsan, Korea The PVA-CN polymer that institute Hyun-Kon doctors Song provide, is bought by Alfa Aesar with manufacturer H61502；LiPF6 (lithium hexafluoro phosphate), 98%；EMC (methyl ethyl ester), 99%, come from Sigma Aldrich, production number 754935；EC (ethylene carbonate), it is anhydrous, come from Sigma Aldrich, production number 676802；And from the porous membranaceous of Asahi companies Object ND420 polyolefin flat membrane-membranoid substance.
The barrier layers Li-BF 120 manufacture in the bag glove that argon gas purges.To bag glove be packed into all material, precision gauge, Then syringe and every other assembly of elements are filled and are emptied four times before electrolyte manufacturing process technique starts.
Organogel electrolyte mixes as follows：4.0ml EMC liquefaction is placed in bottle by being heated to about 140 °F. Then 2.0ml EMC are added into bottle, 0.133g (2wt%) PVA-CN polymer is added in bottle, and by mixture 1 hour is stirred with dissolving PVA-CN.Then 0.133g (2%wt) FEC are added and form additive as SEI, are then added 0.972g(1M)LiPF6And it mixes to complete organogel electrolyte mixture.Then electrolysis cells are assembled in bag glove.With It LiC-GC and washer is in place, anode chamber and cathode chamber are sealed against one another.By organogel electrolyte mixture for soaking LiC- HIPORE membranoid substances are then placed in the cathode side of LiC-GC and use organogel electrolyte mixture to moisten again by the cathode side of GC It is wet.Then cathode disc is placed in the top of organogel mixture.It places the cell inIn bag, and still purged in argon gas Lower sealing.Then by sealing with assembled unitBag is put into 60 DEG C of baking oven 24 hours so that electrolysis Matter gelation.
By electrolysis cells 110 from the bag glove for being removed and placed in argon gas purging in baking oven, and room can be cooled to Temperature.Transparent polypropylene adhesive tape is used to seal the white space above cathode disc and fixed electrode cable.Electrolysis cells 110 are now accurate It is standby ready, it is taken out from bag glove and is connected to electrolyte circulation system.
The lithium of 120g carbonatings in the sulfuric acid of 200ml deionized waters and the 20 weight % of 500ml prepares electrolyte 18.Sulfuric acid is slowly added into lithium carbonate suspension and is sufficiently mixed.Undissolved lithium carbonate is set to settle.It is collected from stoste Supernatant, i.e. the lithium stoste of 18 weight %.The pH measured values of the lithium solution of 18 weight % are 9.By the sulphur for adding 20 weight % Acid reduces pH value of solution.Again, sulfuric acid is slowly added to so that foaming minimizes.The lithium stoste of 18 weight % is adjusted to pH 4.5.Preferred pH is between pH 3.0 and pH 4.5, and most preferably between pH 3.0 and pH 4.0, but the technique can be 7.0 Or it is carried out under lower pH.PH value will lead to occur carbonate in solution higher than 7.0.
Then electrolyte mixture is poured into the circulatory system.Filling circulating pump simultaneously makes solution cycle be let out to check for 30 minutes Leakage.
The electrolyte 18 of rich lithium ion flows through the top half cocurrent of the unit 110 of 114/120 top of LiC-GC-BF multilayers Cross anode 112.When potential is applied to system, lithium metal accumulates in mobile the moon below 114/120 system of LiC-GC-BF multilayers On extremely.
3000 constant potentiometers of Gamry Reference/constant current meter/ZRA is connected to unit 110.In -3 to -6 volts Under voltage, without significant activity.When voltage is increased to -10V, system response.When voltage is increased to 11vdc, ampere Number improves.The deflation of unit anode-side is not observed in 11vdc.Gamry Reference 3000 are not less than- 11vdc.Due to not deflating in -11vdc, so if voltage increases, reduction rate is likely to much higher.If in sun Pole generates negligible oxygen, then higher voltage and reduction rate are preferred.When the time is zero, the pH of electrolyte is 4.46.The pH of solution is down to 4.29 after 35 minutes, and the pH of solution is 4.05 at the end of experiment.The pH value of reduction is indicated from electrolyte Middle removing lithium ion.
Testing the ampere number that -20mA is observed when beginning.After 30 minutes ampere number be slowly increased to- 60mA.Under this value, amperage keeps quite stable to last other 30 minutes.Test timer and figure suspend 30 minutes with Extend experiment (voltage is maintained at -11vdc).After about 65 minutes run times, observed in the anode-side of unit big Ampere peak and sudden violent deflation.This shows that 114/120 membranoid substances of LiC-GC-BF fail.
When unit 110 is opened and 124 side of cathode is exposed to the electrolyte for leaking through LiC-GC-BF114/120, see Rapid degassing and bright white flame are measured, this proves that unit produces lithium gold by the lithium ion being electrolysed in aqueous sulfuric acid Belong to, has passed through LiC-GC-BF114/120 membranoid substance systems.
The disclosure has modified the technique of 2015/0014184 A1 of U.S. Patent Publication to produce with controlled thickness and shape The smooth lithium metal film of high-purity of state.Specifically, battery of the disclosure based on U.S. Patent Publication 2015/0014184A1 The using of the electrical parameter of the middle unit used and material, optimization and variation.
Present disclose provides a kind of, and the lithium based on 2015/0014184 A1 of U.S. Patent Publication produces electrolysis cells, It is assembled in the glove box of argon gas purging, and electrolyte aqueous solution supply container is placed on the outside of the glove box of argon gas purging simultaneously And by being connected to unit equipped with the plastic tube of hydraulic pump and valve.
The disclosure utilizes 3000 constant potentiometers of the Gamry Reference/perseverance electricity for being connected to the unit with reference electrode Flowmeter/ZRA controls applied potential.As described in U.S. Patent application 62/168,770, unit include sleeve and Cell cube.The cross section of moveable cathode crosscutting tool.The Axis Cross of cathode and unit and LIC-GC films can be located at In catholyte above shape object.Anode provides in lower unit body.Unit body portion below LIC-GC membranoid substances is logical Electrolyte that entry load contains lithium ion is crossed, electrolysis is carried out and waste cell melt is discharged via outlet.Lithium ion passes through LIC- GC membranoid substances and catholyte are from the electrolyte conducts containing lithium ion to cathode.Between cathode and embedded cathode and electrolyte LIC-GC membranoid substances separate.LIC-GC membranoid substances include the catholyte for being placed in electrolyte and conducting lithium ions containing lithium ion Li-ion conductive glass ceramics layer (LIC-GC) between matter.The cathode holder driven by servo motor promotes as needed Cathode is to maintain the spacing between the lithium metal formed on cathode and LIC-GC membranoid substances, and takes out cathode to remove lithium Metal.The lithium metal generated at cathode can be extracted as proof gold symbolic animal of the birth year.
Reference electrode is selected from saturation silver chlorate (Ag/AgCl) aqueous solution electrode, free-standing lithium metal foil and copper substrate Lithium metal film.Ag/AgCl electrodes are used as the reference electrode in electrolyte aqueous solution supply container.Independent lithium metal foil and brass Lithium metal film on bottom is used as the reference electrode in the organic bath room of unit.The electrolytic deposition of lithium metal be happened at relative to Ag/AgCl be 3.3V and be 0V relative to Li voltage under.
This disclosure provides a kind of method, wherein lithium is in room temperature or close at room temperature from being separated by inorganic membranoid substance Electrolytic deposition in electrolyte mixture.Inorganic membranoid substance only conducting lithium ions, and impermeable water and other common basal metals are such as The cation of Fe, Ca, Na, K, Cu, Ba and Mg.Lithium cation from containing sulfuric acid and lithium salts (such as lithium carbonate, LiCl, LiF or LiNO3) aqueous solution in pass through membranoid substance (the LiSICON membranoid substances from Ohara), be transferred in dimethyl carbonate 1.0M lithium hexafluoro phosphates (LiPF in (" DMC ")6) organic bath in.Organic bath and cathode contacts.Cathode can be with Including it is any not with lithium at the material such as copper or stainless steel of alloy.The lithium ion for being transmitted through membranoid substance is deposited on cathode with shape At lithium metal film.
The form of lithium metal film can be controlled by the current rate for electro-deposition, as shown in Figure 5.Image in Fig. 5 With -1mA/cm2、–3mA/cm2、–5mA/cm2、–10mA/cm2And -15mA/cm2The SEM for being deposited on the lithium film in copper substrate shines Piece.
As shown in Fig. 5 (A), -1mA/cm2Low current rate cause deposit smooth surface film.On the contrary, -3mA/cm2(as schemed Shown in 5 (B)) and -5mA/cm2The high current rate of (shown in such as Fig. 5 (C)) generates spherical and club shaped structure film respectively.
Fig. 5 is illustrated in copper substrate with 1mA/cm2To 15mA/cm2Current rate generate without dendrite and optically smoothly Lithium film.Copper substrate in Fig. 5 by etching substrate two seconds in the concentrated sulfuric acid (98 weight %), with deionized water rinse substrate with And substrate is air-dried to be pre-processed to substrate, to remove impurity from surface and generate smooth lithium film.
It is -15mA/cm in current rate when using pretreated copper substrate as shown in Fig. 5 (E)2Shi Fasheng dendrite is given birth to It is long.
Fig. 6 show that during 45 minutes 4 hours lithium deposits on the copper dish electrode (13/8 " diameter) of polishing into Journey.In the LiPF of 1.0M6With -1mA/cm in electrolyte solution in DMC2Current density deposited.It is rinsed with DMC Electrode and dry shooting " dry " image after five minutes under argon gas stream.Label on edge comes from is maintained at Organic Electricity by electrode Prevent it from being contacted with LiSICON membranoid substances in electrolyte solutionFolder.As shown in fig. 6, during entire depositing operation (up to 45 minutes 4 hours) can keep the smoothness of lithium film, this corresponds to the deposit of 25 μ m-thicks.These are the result shows that use This method can produce the lithium film of thicker no dendrite.
The smooth lithium metal film of high-purity can be used for needing in ultra-thin, high quality lithium film any application.For example, high-purity The minicell or low work(for the thin high-purity lithium film that smooth lithium metal film can be used for needing to have less than 40 μ m thicks In rate equipment.Minicell including the smooth lithium metal film of high-purity can be with collection of energy electronic equipment (such as piezoelectric electro Sub- equipment and photovoltaic apparatus) coupling, and be desirably integrated into microelectronic device and nano-sensor.The smooth lithium gold of high-purity Belong in the lithium anodes that film can also be used for battery.
The technique of the present invention can deposit 1-50nm, 50-100nm and 100-1000nm and 1-10 μm, 10-100 μm and Lithium film in 100-1000 μ ms.These films also are used as electrochemical capacitor, first capacitor (Metacapacitor), LED Electrode in the TH-42AS700A LED televisions and LED flashlight of video screen such as Panasonic.
The technique of the present invention can also be used for forming (the conjunction of lithium and Al, Ni, Mg, Sn or Si of lithium-metal alloy at room temperature Gold).If being used as cathode at the metal of alloy with lithium by known, lithium will be alloyed into the crystal structure of metal rather than Deposition is on the surface thereof.In the case of Li-Al alloys, the presence of Na or K impurity has shown that reduces room in a linear fashion Toughness and ductility under temperature.Underlying metal content effectively can be reduced to 0ppm by the technique of the present invention.In particular, this hair Bright technique eliminates Na, K, Fe, Ca, Mg and the content of other common metals, therefore is allowed for forming high intensity Li-Al conjunctions The new low temperature path of golden material.

Claims (28)

1. a kind of lithium metal film, wherein the lithium metal film does not have dendrite and is optically smooth.
2. lithium metal film according to claim 1, wherein the lithium metal film carrys out shape using selective lithium ion conduction layer At.
3. lithium metal film according to claim 1, wherein the lithium metal film has about 1nm to about 1000 μm of thickness.
4. lithium metal film according to claim 3, wherein the thickness is about 1nm or higher and is less than about 40 μm.
5. lithium metal film according to claim 3, wherein the thickness is about 25 μm.
6. lithium metal film according to claim 1, wherein the lithium metal film has smooth configuration of surface.
7. lithium metal film according to claim 1, wherein the lithium metal film includes spherical structure.
8. lithium metal film according to claim 1, wherein the lithium metal film includes nanorod structure.
9. a kind of lithium metal film, wherein the lithium metal film is optically smooth, and wherein, d<λ/(8cos θ), Middle d is surface roughness, and λ is the wavelength of incident light, and θ is the incidence angle of incident light.
10. lithium metal film according to claim 9, wherein the surface roughness be measured from reference planes it is square Root roughness height.
11. a kind of electrode comprising：
Substrate；With
The lithium metal film provided on substrate；
Wherein, the lithium metal film does not have dendrite and is optically smooth.
12. electrode according to claim 11, wherein the lithium metal film has about 1nm to about 1000 μm of thickness.
13. electrode according to claim 11, wherein the substrate includes the material at alloy not with lithium.
14. electrode according to claim 11, wherein the substrate includes the material selected from copper and stainless steel.
15. electrode according to claim 11, wherein before providing lithium metal film on substrate, by 98 weights The substrate is etched in the amount % concentrated sulfuric acids two seconds, and the substrate is rinsed with deionized water and is air-dried the substrate come to institute Substrate is stated to be pre-processed.
16. electrode according to claim 11, wherein the lithium metal film carrys out shape using selective lithium ion conduction layer At.
17. a kind of lithium alloy comprising
Substrate；With
The lithium metal film provided on substrate；
Wherein, the lithium metal film does not have dendrite and is optically smooth, and
Wherein, the substrate includes the material at alloy with lithium.
18. lithium alloy according to claim 17, wherein the substrate includes aluminium.
19. lithium alloy according to claim 17, wherein the substrate includes the material selected from silicon and tin.
20. lithium alloy according to claim 17, wherein the substrate includes the material selected from carbon, titanium, magnesium and bismuth.
21. lithium alloy according to claim 17, wherein the lithium metal film carrys out shape using selective lithium ion conduction layer At.
22. a kind of battery comprising
Cathode；
Anode；And
Electrolyte,
Wherein, at least one upper offer lithium metal film of cathode and anode, and
Wherein, the lithium metal film does not have dendrite and is optically smooth.
23. battery according to claim 22, wherein the battery is selected from following：Lithium primary battery, secondary cell and micro- Type battery.
24. battery according to claim 22, wherein the lithium metal film has about 1nm to about 1000 μm of thickness.
25. battery according to claim 22, wherein the lithium metal film carrys out shape using selective lithium ion conduction layer At.
26. a kind of method for the desired form obtaining lithium metal film comprising
Using selective lithium ion conduction layer electrolytic deposition lithium metal, and
The current rate of electrolytic deposition is controlled to obtain desired form.
27. according to the method for claim 26, wherein current rate is controlled in -1mA/cm2To -10mA/cm2Range It is interior.
28. according to the method for claim 26, wherein current rate is controlled in -1mA/cm2To -4.5mA/cm2Range It is interior.
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